Monazo dyes from pyrazolones and aminobenzene-polysulphonic acids



' Patented Oct. 16, 1928.

1 UNITED STATES PATENT OFFICE.

LEON W. vGELIILLEIR, OF HAMBURG, NEW YORK, ASSIGNOR TO NATIONAL ANILINE & CHEMICAL (30., INCL, OF NEW YORK, N. Y.,'A CORPORATION OF NEW YORK.

MonAzo nYEs FROM rYRAzoLoNEs Ann No Drawing Application filed December This invention relates to the manufacture and production of new azo coloring matters of the pyrazolone series which are of value for dyeing wool andother material. Material dyed with one or more of the new dyestuffs also constitutes a part of the present invention. I

According to the present invention, it has been found that new and val'uable' azo dyestufis can be obtained by coupling a diazotized aniline polysulphonic acid, more particularly a diazotized aniline disulphonic acid, into a l-aryl-5-pyrazolone body of the benzene or naphthalene or other aromatic series which maycontai'n substituents in the aryl radical.

The new coloring matters are no pyrazolone compounds which contain the following probable atomic grouping:

it N N=(lR wherein R signifies a methyl or a carboxyl group, and R represents a polysulphonated benzene nucleus which is free from other substituents. They also correspond with the formula RN=NR wherein R signifies a 1-aryl-5-pyrazolone nucleus which may contain substituents in the aryl radical, and B represents a polysulphonated benzene nucleus which is free from other substituents. In the dried and pulverized'state and in the form of their sodium salts they constitute yellow to red to brown powders soluble in concentrated sulphuric acid, soluble in water giving yellow to red to brown colorations and dye wool yellow to red to brown shades. Upon reduction, for example with stannous chloride and hydrochloric acid, they yield a .polysulphonated aniline and a 1-aryl-4-amino-5- pyrazolone body.

The following specific example will 'fur-, ther illustrate the invention, but it will be understood that it is not limited thereto. The parts are by weight.

EwampZe.-177 parts of aniline-.ZA-disulphonic acid are dissolved in 1500 parts water and 1&0 parts of B. sulphuric acid, and the iced solution is diazotized by means of about e9 parts of sodium nitrite. The diazo solution thus obtained is introduced into a AMINOBENZENE-IOLYSULPHONIC ACIDS.

23,1925. Serial No. 77,375. I

solution, maintainedat about 159-25 (1., of 2113 parts of the monosodium salt of 1-(2- methyl-4-sulphophenyl) -3-carboxy .5} pyra 7 zolone dissolved in about 3000 parts water and sufficient sodium carbonate to maintain an alkaline reaction during the combination. hen the combination is complete, the soluti-on'is acidified with hydrochloric acid and the dyestuif salted out by the addition of common salt, filtered oii' and dried. Insteadof N N I C-COOH CO- H-N-N SOIH HOzS . SOzH It constitutes a yellow powder, soluble in concentrated sulphuric acid and soluble in Water, and dyes Wool from an acid bath ellow shades of good fastness to light an to washing. Upon reduction it yields aniline- 2.4-disulphonic acid and.1-(2'-methyl-4-sulphophenyl) 3-carboXy-4-am1n0-5-pyrazol0ne.

In a similar manner, the diazo compounds of other aniline polysulphonic acids can be used such as, for example, aniline-2.5-disulphonic acid, aniline-3.5-disulphonic acid, etc. For instance, the dye from aniline-3.5-disul-. phonic acid and l-(2-methyl-4'-sulpho-- 'phenyl)-3-methyl-5-pyrazolone has the following probable formula:

Boas v SOaH In the specification and claims it will b understood that the pyrazolon'e bodies contemplated in the present invention carry a methyl or a carboxyl group in the 3'-p0sition of the pyrazolone nucleus unless otherwise specified, and are capable of combining in t-position with diazo compounds.

I claim:

1. Asnew products, the azo pyrazolone coloring matters which contain the probable atomic grouping:

wherein R represents a methyl or a carboxyl group, and R signifies a polysulphonated benzene nucleus which is free from other substituents. a

2. A composition of matter comprising an azo pyrazolone compound which contains the probable atomic grouping:

N (|3R V OO-CHN=N-R wherein R represents a methyl or a carboxyl group, and R signifies a di-sulphonated ben- 4. As new products, the azo pyrazolonecoloring matters which in the free state correspond with the probable formula:

SOaH

. wherein R signifies an aryl-pyrazolone body of the benzene series which contains a sulphonic acid group in the phenyl nucleus.

5. As a new product, the monazo pyrazolone dyestuff which in the free state COltre-. sponds with the probable formula:

6. Material dyed with a coloring matter of claim 1. p 1 V 7. Material dyed with a coloring matter of claim 2.

8. Material dyed with a coloring matter of claim 3.

9. Material dyed with afcoloring matter of claim 4. i

10. Material dyed with the coloring mat LEQN w. :GE LER. I I 

